US10766913B2 - Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof - Google Patents

Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof Download PDF

Info

Publication number
US10766913B2
US10766913B2 US16/140,573 US201816140573A US10766913B2 US 10766913 B2 US10766913 B2 US 10766913B2 US 201816140573 A US201816140573 A US 201816140573A US 10766913 B2 US10766913 B2 US 10766913B2
Authority
US
United States
Prior art keywords
siloxanes
acid
mixtures
siloxane
units
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
US16/140,573
Other languages
English (en)
Other versions
US20190106441A1 (en
Inventor
Wilfried Knott
Horst Dudzik
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Assigned to EVONIK DEGUSSA GMBH reassignment EVONIK DEGUSSA GMBH ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: DUDZIK, HORST, KNOTT, WILFRIED
Publication of US20190106441A1 publication Critical patent/US20190106441A1/en
Assigned to EVONIK OPERATIONS GMBH reassignment EVONIK OPERATIONS GMBH CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: EVONIK DEGUSSA GMBH
Application granted granted Critical
Publication of US10766913B2 publication Critical patent/US10766913B2/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/12—Polysiloxanes containing silicon bound to hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42—Block-or graft-polymers containing polysiloxane sequences
    • C08G77/44—Block-or graft-polymers containing polysiloxane sequences containing only polysiloxane sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0834—Compounds having one or more O-Si linkage
    • C07F7/0838—Compounds with one or more Si-O-Si sequences
    • C07F7/0872—Preparation and treatment thereof
    • C07F7/0876—Reactions involving the formation of bonds to a Si atom of a Si-O-Si sequence other than a bond of the Si-O-Si linkage
    • C07F7/0878—Si-C bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3893—Low-molecular-weight compounds having heteroatoms other than oxygen containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/08—Preparatory processes characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/06—Preparatory processes
    • C08G77/10—Equilibration processes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04—Polysiloxanes
    • C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/70—Siloxanes defined by use of the MDTQ nomenclature

Definitions

  • the invention relates to a process for preparing mixtures of cyclic branched siloxanes of the D/T type, to the mixtures of cyclic branched siloxanes of the D/T type themselves, and to the methods of processing these siloxanes to give functionalized branched siloxanes and/or branched silicone oils.
  • organomodified siloxanes especially branched function-bearing siloxanes
  • a difficulty frequently encountered is that competing processes that take place simultaneously in the reaction matrix can adversely affect the quality of the desired product.
  • Polyorganosiloxanes are prepared according to the prior art by hydrolysis and condensation proceeding from methylchlorohydrosilanes having mixed substitution.
  • Direct hydrolytic condensation of hydrogen-containing silanes for example dimethylmonochlorosilane or methyldichlorosilane, is described, for example, in U.S. Pat. No. 2,758,124.
  • the siloxane phase that separates in the hydrolysis is separated from the water phase having a hydrochloric acid content.
  • DE 1125180 describes an improved process utilizing an organic auxiliary phase, in which the hydrosiloxane formed is present as a separate phase dissolved in an organic solvent and, after separation from the acidic water phase and distillative removal of the solvent, is resistant to gelation.
  • a further process improvement with regard to minimized solvent input is described by EP0967236, the teaching of which involves first using only small amounts of water in the hydrolytic condensation of the organochlorosilanes, such that hydrogen chloride is driven out in gaseous form in the first step and can be sent directly to further end uses as a material of value.
  • Branched organomodified polysiloxanes can be described by a multitude of structures. In general, a distinction has to be made between a branch or crosslink which is introduced via the organic substituents and a branch or crosslink within the silicone chain.
  • Organic crosslinkers for linkage of siloxane skeletons bearing SiH groups are, for example, ⁇ , ⁇ -unsaturated diolefins, divinyl compounds or diallyl compounds, as described, for example, in U.S. Pat. No. 6,730,749 or EP 0381318.
  • This crosslinking by platinum-catalysed hydrosilylation downstream of the equilibration means an additional process step in which both intramolecular linkages and intermolecular linkages can take place.
  • the product properties are additionally greatly affected by the different reactivities of the low molecular weight organic difunctional compounds that have a tendency to peroxide formation.
  • EP 0 675151 describes the preparation of a polyethersiloxane by hydrosilylation of a hydrosiloxane with a deficiency of hydroxy-functional allyl polyether, in which unconverted SiH functions are joined to the hydroxyl groups of the polyether substituents via an SiOC bond with addition of sodium methoxide.
  • the increase in molar mass leads to broad scatter in the product properties, for example the viscosity.
  • Branching within the siloxane chain therefore already has to be effected in the course of production of the hydrosiloxane, in order to get round the described disadvantages of the crosslinking.
  • Branches within the siloxane chain require the synthetic incorporation of trifunctional silanes, for example trichlorosilanes or trialkoxysilanes.
  • a trifunctional low molecular weight hydrosiloxane is prepared by hydrolysis and condensation from 1,1,3,3-tetramethyldisiloxane and methyltriethoxysilane, as taught, for example, by DE 3716372. Only in a second step is equilibration then possible with cyclic siloxanes to give higher molar masses, as explained by DE 102005004676. For further conversion—and therefore only in a third step—the singly branched hydrosiloxane thus prepared can be provided by the methods known per se for functionalization of siloxane compounds having SiH groups with organic substituents.
  • a further option described in U.S. Pat. No. 6,790,451 is that of preparing a copolymer from trichloromethylsilane or trialkoxymethylsilane with hexamethyldisiloxane or trimethylchlorosilane, also called MT polymer therein, which is equilibrated in a second step together with a polydimethyl(methylhydro)siloxane copolymer.
  • the preparation of such MT polymers entails the use of strong bases or strong acids, in some cases in combination with high reaction temperatures, and results in prepolymers of such high viscosity that the neutralization thereof is made considerably more difficult and hence further processing to give end products of constant composition and quality is significantly limited.
  • EP 0675151 first of all, the hydrolysis and condensation of the SiH-free branched silicone polymer is conducted in xylene in such a way that the final occlusion of the precondensate is conducted with a large excess of hexamethyldisiloxane and, in the second step, the equilibration is undertaken with methylhydropolysiloxane to give a branched hydrosiloxane (preparation method 6, ibid.).
  • the teaching of EP 0675151 relates to a procedure for preparation of non-SiH-functional branched siloxanes including merely a partial condensation of the methyltrichlorosilane used (preparation method 7, ibid.).
  • these two procedural strategies do not address the need for a universally utilizable preparation method for branched siloxanes.
  • WO2009065644 A1 teaches a process for preparing branched SiH-functional siloxanes by reacting a mixture comprising
  • Scott speculates that his compounds having D-T structures contain T structural elements joined directly to one another and not via D units.
  • the interpretation of the results in Scott is based on the premise that all the SiC bonds present in the co-hydrolysate withstand the severe thermal treatment that he chose.
  • Makarova et al. (Polyhedron Vol. 2, No. 4, 257-260 (1983)) prepared 10 oligomeric methylsiloxanes having cyclic and linear segments by the controlled low-temperature condensation of siloxanes having SiOH groups and containing SiCl groups in the presence of organic amines such as triethylamine or aniline in benzene or diethyl ether as solvents, separated off the precipitated amine hydrochlorides, and washed and then fractionally distilled the crude reaction products. Subsequently, the bicyclic methylsiloxanes were subjected to pyrolysis at temperatures between 400 and 600° C., and the pyrolysis products were characterized by gas chromatography.
  • organic amines such as triethylamine or aniline in benzene or diethyl ether
  • the low molecular weight compounds used in the course of this study for example hydroxynonamethylcyclopentasiloxane, hydroxyheptamethylcyclotetrasiloxane, dihydroxytetramethyldisiloxane, from the point of view of the silicone chemistry conducted on the industrial scale, are to be considered as exotic species of purely academic interest.
  • the pure-chain siloxane compounds of the D/T type defined in terms of molar mass that have been synthesized by this route are unsuitable for the production of organomodified siloxanes that are employed in demanding industrial applications, for example in PU foam stabilization or in the defoaming of fuels, etc.
  • Active ingredients that effectively address such a field of use are always characterized by a broad oligomer distribution comprising high, moderate and low molar masses, since the oligomers present therein, depending on their molar mass and hence their diffusion characteristics, can very commonly be imputed to have differentiated surfactant tasks in different time windows of the respective process.
  • the as yet unpublished European patent application number 17156421.4 is geared to a preparation process for obtaining branched organomodified siloxanes, which comprises (a) in a first step preparing cyclic branched siloxanes of the D/T type by the reaction of trialkoxysilane exclusively with siloxane cycles and/or ⁇ -dihydroxypolydimethylsiloxane in a solvent and (b) in a second step undertaking the functionalization of these cyclic branched siloxanes by acidic equilibration with functional silanes and/or siloxanes.
  • the mixtures of cyclic branched siloxanes having exclusively D and T units and having no functional groups that arise from the first step are characterized in that the cumulative proportion of the D and T units having Si-alkoxy and SiOH groups that are present in the siloxane matrix, determinable by 29 Si NMR spectroscopy, is less than or equal to 2 mole percent, and so no significant proportions of the Si-alkoxy or SiOH groups that originate from the first stage are carried through into the second step and molecularly conserved.
  • silicon-free solvents including liquid (alkyl)aromatics, for example toluene, the isomeric xylenes, cycloaliphatics, for example cyclohexane, but also diethyl carbonate, are used, more preferably toluene.
  • liquid (alkyl)aromatics for example toluene
  • the isomeric xylenes for example cyclohexane, but also diethyl carbonate
  • This process comprises an acid-catalysed equilibration of trialkoxysilanes with siloxane cycles and/or ⁇ dihydroxypolydimethylsiloxane in the presence of at least one acidic catalyst and, thereafter, a hydrolysis and condensation reaction initiated by addition of water with subsequent use of a silicon-containing solvent, followed by a distillative removal of the alcohol released, water present in the system and silicon-containing solvent, and by a neutralization or removal of the acidic catalyst and, if appropriate, removal of any salts formed.
  • the advantage of the as yet unpublished European patent application with reference number 17169876.4 is that the solvent mixtures obtained in the course of the production of cyclic branched DT siloxanes are simpler in nature than those obtained after the process of the likewise as yet unpublished patent application under reference number 17156421.4.
  • solvent systems consisting of toluene/ethanol/water or else of ethanol/toluene
  • the process conducted in silicon-containing solvents requires, for example, merely the thermal removal of ethanol/water mixture.
  • the process according to the invention especially envisages conducting the acid-catalysed equilibration of trialkoxysilanes with siloxane cycles and/or ⁇ -dihydroxypolydimethylsiloxane, with subsequent addition of water and simple siloxane cycles that function as solvent and subsequent distillative removal of an alcohol/water mixture, and then, after addition of toluene, by distillative removal of a toluene/water mixture, driving the equilibrating incorporation of the simple siloxane cycles that functioned as solvent beforehand and the hydrolysis and condensation reaction to such an extent that the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29 Si NMR spectroscopy, is not more than than 2 mole percent.
  • the combined, successive use of silicon-containing and silicon-free solvents is found to be particularly advantageous since it allows the removal of an alcohol/water mixture which is easy to dispose of and the clean removal of the toluene process solvent, since the toluene/water mixture removed by distillation separates in a fully density-separated manner in condensed phase.
  • This does justice to the important idea of recycling, since the very pure toluene separated out (in this regard, see the gas chromatography analysis of Inventive Example 1), if required, can easily be sent back into the process.
  • the mixtures of cyclic branched siloxanes of the D/T type produced by the process according to the invention which have a proportion of Si-alkoxy or SiOH determined by spectroscopy of not more than 2 mole percent based on the totality of silicon detected by spectroscopy, permit processing to give the corresponding functionalized branched siloxanes and/or branched silicone oils under acid-catalysed equilibration without adjustment of customary standard equilibration conditions (such as preferably: 0.1% by weight of added trifluoromethanesulfonic acid, 40° C. ⁇ reaction temperature ⁇ 60° C., reaction time 6 hours), which incidentally corresponds to a preferred embodiment of the process according to the invention.
  • customary standard equilibration conditions such as preferably: 0.1% by weight of added trifluoromethanesulfonic acid, 40° C. ⁇ reaction temperature ⁇ 60° C., reaction time 6 hours
  • the present invention combines both the advantage of making cyclic branched siloxane mixtures of the D/T type available with a high degree of condensation and hence easy further processibility and the advantage, from the point of view of sustainability, of giving rise to only a small amount of wastes that are additionally easy to dispose of.
  • a particular additional advantage of the invention is that the mixtures according to the invention additionally feature excellent storage stability, even in the case of storage under air and at high temperatures. Solidification or even through-curing does not occur, even after storage under air at elevated temperatures for a number of months.
  • the invention provides mixtures of cyclic branched siloxanes having exclusively D and T units, with the proviso that the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29 Si NMR spectroscopy, is less than 2 mole percent, preferably less than 1 mole percent, and further comprising at least 5% by weight of siloxane cycles, such as preferably octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ), dodecamethylcyclohexasiloxane (D 6 ) and/or mixtures thereof.
  • the siloxanes prepared in accordance with the invention do not have any further functional groups.
  • the invention further provides a process for preparing mixtures of cyclic branched siloxanes having exclusively D and T units, preferably according to any of claims 1 - 5 , comprising
  • This process especially enables the provision of the mixtures according to claim 1 .
  • the invention still further provides a process for producing branched organomodified siloxanes
  • cyclic branched siloxanes are provided in a first step, preferably mixtures of cyclic branched siloxanes having exclusively D and T units, with the proviso that the cumulative proportion of the D and T units having Si-alkoxy and/or SiOH groups that are present in the siloxane matrix, determinable by 29 Si NMR spectroscopy, is less than 2 mole percent, preferably less than 1.0 mole percent, and further comprising at least 5% by weight of siloxane cycles, such as preferably octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ) and/or mixtures thereof, and wherein, in a second step, the cyclic branched siloxanes are equilibrated under acidic conditions with silanes and/or siloxanes.
  • the ratio of D to T units is between 10:1 and 3:1, preferably between 6:1 and 4:1.
  • the molar mass ratio M w /M n of the mixture of cyclic branched siloxanes having exclusively D and T units is in the range of 2 ⁇ M w /M n ⁇ 50.
  • GPC gel permeation chromatography
  • the branching T unit derives from alkyltrialkoxysilanes and/or, preferably or, phenyltrialkoxysilanes, this is a further preferred embodiment of the invention.
  • a preferred embodiment of the invention is likewise when the branching T unit derives from methyltriethoxysilane.
  • the silicon-containing solvent to be used here preferably comprises the isomeric siloxane cycles octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ) and/or mixtures thereof, and it is advantageous to work in mass ratios of silicon-containing solvent to the siloxane of 1:1 to 5:1. This corresponds to a preferred embodiment of the invention.
  • the acidic catalyst used is para-toluenesulfonic acid, trifluoromethanesulfonic acid, trichloroacetic acid, sulfuric acid, perchloric acid, phosphoric acid and/or hexafluorophosphoric acid, preferably in amounts of 0.1 to 2.0 percent by weight, more preferably in amounts of 0.15 to 1.0 percent by weight, based in each case on the silicon-containing component of the reaction matrix.
  • the acidic catalyst used is a macrocrosslinked sulfonic acid ion exchange resin, preferably in amounts of 1.0 to 10.0 percent by weight, more preferably in amounts of 2.0 to 6.0 percent by weight, based in each case on the silicon-containing component of the reaction matrix.
  • reaction according to the invention is conducted at temperatures in the range from 20° C. to 120° C., preferably from 40° C. to 110° C., this is a further preferred embodiment of the invention.
  • reaction comprises a preliminary equilibration step at temperatures of T>40° C., followed by a condensation initiated by addition of water at temperatures of T>60° C., where the water is added in one portion, in several portions or continuously.
  • Trialkoxysilanes used may especially be those in which the alkoxy radicals are all the same or all different or in which some are the same.
  • Trialkoxysilanes used may especially be triethoxysilanes, preferably methyltriethoxysilane, alkyltriethoxysilanes, for example n-propyltriethoxysilane, isobutyltriethoxysilane, pentyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, hexadecyltriethoxysilane, n-octadecyltriethoxysilane, halogenated or pseudohalogenated alkyltrialkoxysilanes, especially alkyltriethoxysilanes, for example chloropropyltriethoxysilane,
  • the equilibration of methyltriethoxysilane is undertaken exclusively with siloxane cycles and/or ⁇ dihydroxypolydimethylsiloxane with addition of a catalytic amount of preferably trifluoromethanesulfonic acid at 60° C. over the course of 2 to 4 hours.
  • the condensation reaction is then conducted over the course of preferably 2 to 4 hours at preferably 80° C., then another portion of water is preferably added to the system, in order then to add a silicon-containing solvent, preferably simple siloxane cycles (D 4 /D 5 ), and to conduct the distillative removal of ethanol/water mixtures until attainment of an internal temperature of 90° C.
  • a silicon-containing solvent preferably simple siloxane cycles (D 4 /D 5 )
  • Toluene is then added to the reaction mixture and the water still present in the system is removed by distillation up to a bottom temperature of 100° C., preferably at the water separator.
  • reaction mixture is allowed to cool down to about 60° C., the acid is neutralized, for example by addition of solid sodium hydrogencarbonate, and the mixture is then stirred for complete neutralization for a further 30 minutes. After cooling to 25° C., salts are removed by filtration, for example sodium triflate. At 70° C. and with an auxiliary vacuum of ⁇ 1 mbar applied, the toluene used as solvent is distilled off.
  • the amount of water that has been introduced here into the system is preferably such that the total amount of water used over all the steps of the process according to the invention covers a stoichiometric excess of 150% to 500%, preferably 150% to 250%, based on methyltriethoxysilane used.
  • the trifluoromethanesulfonic acid which is used with preference as equilibration catalyst in the process according to the invention, is preferably used in amounts of 0.1%-0.5% by weight, preferably in amounts of 0.15% to 0.3% by weight, based on the mass of all Si-containing reactants in the equilibration mixture.
  • a crucial advantage of the preparation process according to the invention is that the synthesis of cyclic branched siloxanes can be conducted under more severe reaction conditions, for example at a high acid concentration and high temperatures, without product damage since there are no sensitive moieties present at all (for example SiH functions).
  • Optimal incorporation of branching units (T structures) into the molecular skeletons of the siloxane oligomers is thus possible, where the T structures are ideally separated by D units in each case and are not present in cumulated form in a domain-like manner, as shown by the 29 Si NMR spectroscopy, especially in the shift region of the T structures.
  • the silicon-containing solvents usable here with preference in accordance with the invention include the simple liquid dimethylsiloxane cycles such as octamethylcyclotetrasiloxane (D 4 ) and decamethylcyclopentasiloxane (D 5 ), and mixtures thereof. Particular preference is given to decamethylcyclopentasiloxane (D 5 ).
  • the silicon-containing solvent especially comprising the simple siloxane cycles mentioned, as already described above, is partly incorporated into the siloxanes having exclusively D and T units after addition of toluene and in the course of the distillative removal of a toluene/water mixture.
  • the acidic catalyst used in accordance with the invention should be removed prior to the final distillative removal of the toluene still present in the system, either by a neutralization in which any salts formed are to be removed or by a simple removal from the system (for example using macrocrosslinked sulfonic acid ion exchange resins).
  • a multitude of bases are suitable for neutralization.
  • sodium hydrogencarbonate is an effective base for neutralization of the trifluoromethanesulfonic acid which is present in the system and is used with preference in accordance with the invention.
  • the resulting mixtures usually comprise at least 5% by weight of siloxane cycles, such as preferably octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ) and/or mixtures thereof.
  • siloxane cycles such as preferably octamethylcyclotetrasiloxane (D 4 ), decamethylcyclopentasiloxane (D 5 ) and/or mixtures thereof.
  • a further embodiment of the process claimed which is preferred in accordance with the invention arises from the use of a water-containing macroporous sulfonic acid polystyrene resin, for example of a Lewatit® K 2621 wetted with 10% by weight of water, for equilibration.
  • An example of a particularly preferred sulfonic acid cation exchange resin is Lewatit® K 2621.
  • siloxane structure i.e. to provide branched organomodified siloxanes, an acidic equilibration with silanes, preferably functional silanes, and/or siloxanes is conducted.
  • silanes and/or siloxanes used may be any acid-equilibratable silicon compounds. Functional silanes and/or siloxanes are preferred.
  • Functional silane/siloxane are understood in this connection to mean all those compounds comprising one silicon atom and/or multiple silicon atoms which can be incorporated into the copolymer by way of acidic equilibration. More particularly, these acid-equilibratable silanes or siloxanes, as well as any hydrogen, alkyl or aryl, or vinyl substituents present, also have hydroxyl, alkoxy and chlorine substituents. Likewise suitable are functional silanes/siloxanes that bear acidic moieties, for example toluenesulfonate, trifluoromethylsulfonate and sulfate radicals.
  • the silanes used may especially be diethoxydimethylsilane, trimethylalkoxysilanes and/or dimethyldichlorosilane.
  • the siloxanes used may especially be tetramethyldisiloxane, ⁇ -dihydropolydimethylsiloxanes, poly(methylhydro)siloxanes, ⁇ -dialkoxypolydimethylsiloxanes and/or ⁇ -divinylpolydimethylsiloxanes.
  • branched silicone oils are obtainable by the acidic co-equilibration of the cyclic branched siloxane of the D/T type obtained in the first step with hexamethyldisiloxane and/or polydimethylsiloxanes.
  • cyclic branched siloxanes are reacted with polydimethylsiloxanes or hexamethyldisiloxane.
  • Suitable acidic catalysts are the strong acids (equilibrating acids) known from the prior art for siloxanes, i.e. mineral acids, for example sulfuric acid, but also sulfonic acids, fluoroalkylsulfonic acids, for example trifluoromethanesulfonic acid, acidic aluminas or acidic ion exchange resins, for example the products known by the Amberlite®, Amberlyst® or Dowex® and Lewatit® brand names.
  • mineral acids for example sulfuric acid
  • fluoroalkylsulfonic acids for example trifluoromethanesulfonic acid
  • acidic aluminas or acidic ion exchange resins for example the products known by the Amberlite®, Amberlyst® or Dowex® and Lewatit® brand names.
  • zeolites for example zeolites, montmorillonites, attapulgites, bentonites and other aluminosilicates
  • synthetic ion exchangers are preferably solids (usually in granular form) with a three-dimensional, water-insoluble, high molecular weight matrix based on phenol-formaldehyde resins or copolymers of styrene-divinylbenzene into which numerous “anchor groups” of different acidity have been incorporated.
  • Acidic ion exchangers used advantageously may include those as described in EP 1439200 B1.
  • these siloxane cycles can be removed by simple distillation and recycled.
  • the branched organomodified siloxanes recovered by acidic equilibration from the second step are suitable as starting material for production of stabilizers for PUR foams, for production of defoamers, for production of paint additives, for production of emulsifiers, especially of cosmetic emulsifiers, for production of cosmetic conditioners, for production of deaerating agents, for production of demulsifiers, for production of textile finishes, for production of building protection additives, for production of polymer additives, especially anti-scratch additives, for production of antifouling additives or coatings and for production of anti-icing coatings.
  • This use forms a further part of the subject-matter of the present invention.
  • SiC-bonded final products are obtainable via hydrosilylation, or else SiOC-bonded final products are obtainable via dehydrogenative SiOC bond formation or condensation by the known methods of silicone chemistry.
  • TMS tetramethylsilane
  • the weight-average molar mass M w and the molar mass distribution M w /M n are determined in the context of this invention using an EcoSEC GPC/SEC instrument from TOSOH Bioscience GmbH by gel permeation chromatography from toluenic solutions of the siloxanes.
  • a Micro SDV 1000/10000 column of length 55.00 cm is used, combined with an EcoSEC RI detector (dual flow refractive index detection).
  • the polystyrene standard covers the molar mass range from 162 g/mol to 2 520 000 g/mol.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Silicon Polymers (AREA)
US16/140,573 2017-10-09 2018-09-25 Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof Active US10766913B2 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP17195510 2017-10-09
EP17195510.7A EP3467006B1 (de) 2017-10-09 2017-10-09 Mischungen zyklischer-verzweigter siloxane vom d/t-typ und deren folgeprodukte
EP17195510.7 2017-10-09

Publications (2)

Publication Number Publication Date
US20190106441A1 US20190106441A1 (en) 2019-04-11
US10766913B2 true US10766913B2 (en) 2020-09-08

Family

ID=60190549

Family Applications (1)

Application Number Title Priority Date Filing Date
US16/140,573 Active US10766913B2 (en) 2017-10-09 2018-09-25 Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof

Country Status (4)

Country Link
US (1) US10766913B2 (de)
EP (1) EP3467006B1 (de)
CN (1) CN109627444B (de)
CA (1) CA3020081A1 (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11286366B2 (en) 2019-05-28 2022-03-29 Evonik Operations Gmbh Process for recycling silicones
US11345783B2 (en) 2018-05-17 2022-05-31 Evonik Operations Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers of the structure type ABA
US11359056B2 (en) 2018-05-17 2022-06-14 Evonik Operations Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers of the structure type ABA
US11498996B2 (en) 2019-05-28 2022-11-15 Evonik Operations Gmbh Process for producing polyoxyalkylene polysiloxane block polymers
US11591448B2 (en) 2020-03-27 2023-02-28 Evonik Operations Gmbh Physical reutilization of siliconized sheets
US11732092B2 (en) 2020-10-19 2023-08-22 Evonik Operations Gmbh Upcycling process for processing silicone wastes
US11795275B2 (en) 2018-12-04 2023-10-24 Evonik Operations Gmbh Reactive siloxanes
US11859053B2 (en) 2020-02-14 2024-01-02 Evonik Operations Gmbh SiOC-bonded, linear polydimethylsiloxane-polyoxyalkylene block copolymers
US12060460B2 (en) 2021-04-29 2024-08-13 Evonik Operations Gmbh Process for producing endcapped, liquid siloxanes from silicone wastes
US12152109B2 (en) 2020-12-09 2024-11-26 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes
US12460081B2 (en) 2021-11-25 2025-11-04 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes
US12577351B2 (en) 2021-07-14 2026-03-17 Evonik Operations Gmbh Increasing the molecular weight of low molecular weight alpha,omega-polysiloxanediols

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10787464B2 (en) 2017-10-17 2020-09-29 Evonik Operations Gmbh Zinc ketoiminate complexes as catalysts for the production of polyurethanes
ES2901137T3 (es) 2017-11-29 2022-03-21 Evonik Operations Gmbh Procedimiento para la producción de polietersiloxanos enlazados a SiOC ramificados en la parte de siloxano
EP3611215A1 (de) 2018-08-15 2020-02-19 Evonik Operations GmbH Verfahren zur herstellung acetoxygruppen-tragender siloxane
EP3611214A1 (de) 2018-08-15 2020-02-19 Evonik Operations GmbH Sioc-verknüpfte, lineare polydimethylsiloxan-polyoxyalkylen-blockcopolymere
ES2986717T3 (es) 2019-05-28 2024-11-12 Evonik Operations Gmbh Procedimiento para la producción de polietersiloxanos enlazados a SiOC ramificados en la parte de siloxano
EP3744753B1 (de) 2019-05-28 2022-04-06 Evonik Operations GmbH Verfahren zur aufreinigung von acetoxysiloxanen
EP3744756B1 (de) 2019-05-28 2024-07-03 Evonik Operations GmbH Acetoxysysteme
ES2992917T3 (en) 2019-05-28 2024-12-19 Evonik Operations Gmbh Method for producing siloxanes bearing acetoxy groups
EP3744760A1 (de) 2019-05-28 2020-12-02 Evonik Operations GmbH Verfahren zur herstellung von im siloxanteil verzweigten sioc-verknüpften polyethersiloxanen
EP3744761B1 (de) * 2019-05-28 2021-06-30 Evonik Operations GmbH Sioc basierte polyethersiloxane
EP3744755B1 (de) 2019-05-28 2024-10-09 Evonik Operations GmbH Verfahren zur herstellung acetoxygruppen-tragender siloxane
DK3744763T3 (da) 2019-05-28 2024-11-04 Evonik Operations Gmbh Skræddersyede sioc baserede polyethersiloxaner
EP3744745A1 (de) 2019-05-28 2020-12-02 Evonik Operations GmbH Herstellung von pu-schaumstoffen
CN112774960B (zh) * 2020-12-18 2023-09-26 大唐浑源密马鬃梁新能源有限公司 一种适应于高寒地区防覆冰风机叶片涂层工艺
CN117586504A (zh) 2022-08-12 2024-02-23 赢创运营有限公司 由废硅酮制备烷氧基硅氧烷的方法
US20240052107A1 (en) 2022-08-12 2024-02-15 Evonik Operations Gmbh Production of alkoxysiloxanes
US20240052108A1 (en) 2022-08-12 2024-02-15 Evonik Operations Gmbh Production of alkoxysiloxanes

Citations (105)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093101A (en) 1990-09-04 1992-03-03 Th. Goldschmidt Ag Method for the preparation of active magnesium hydride-magnesium-hydrogen storage systems and apparatus for carrying out the method
EP0514737A1 (de) 1991-05-24 1992-11-25 Th. Goldschmidt AG Verfahren zur Herstellung von Organopolysiloxanen mit mindestens einer an ein Si-Atom gebundenen Cyclopentadienylgruppe
US5198207A (en) 1990-12-08 1993-03-30 Th. Goldschmidt Ag Method for the preparation of active magnesium hydride-magnesium hydrogen storage systems, which reversibly absorb hydrogen
US5221499A (en) 1991-05-18 1993-06-22 Th. Goldschmidt Ag Method for the preparation of dialkylmagnesium compounds by the reaction of magnesium hydride with an olefin
US5371161A (en) 1992-11-21 1994-12-06 Th. Goldschmidt Ag Method for the preparation of organopolysiloxanes containing SIH groups
US5430166A (en) 1993-06-24 1995-07-04 Th. Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US5455367A (en) 1993-04-22 1995-10-03 Th. Goldschmidt Ag Method for the synthesis of silanes or organosilicon hydrides by the reduction of the corresponding silicon halides or organosilicon halides
EP0685425A1 (de) 1994-06-03 1995-12-06 Th. Goldschmidt AG Verfahren zur Herstellung von Magnesium-hydrid
US5475127A (en) 1994-04-27 1995-12-12 Th. Goldschmidt Ag Organosilyl and organosiloxanyl derivatives of glycerin ethers and their use
US5565183A (en) 1993-10-27 1996-10-15 Th. Goldschmidt Ag Method for the preparation of aluminum hydride (AlH3) by reacting magnesium hydride with aluminum halide
US5670129A (en) 1994-12-24 1997-09-23 Th. Goldschmidt Ag. Method for synthesizing aluminum hydride
US5831103A (en) 1992-10-20 1998-11-03 Th. Goldschmidt Ag Halogen-magnesium-aluminum hydridohalides, methods for their synthesis and their use as reducing agents
US5856548A (en) 1997-05-17 1999-01-05 Th. Goldschmidt Ag Process for preparing dimethylmonochlorosilane
US5934579A (en) 1996-04-03 1999-08-10 Th. Goldschmidt Ag Apparatus for treating suspensions
US5951739A (en) 1995-05-26 1999-09-14 Th. Goldschmidt Ag Process for preparing x-ray amorphous and nanocrystalline metal powders
US5972285A (en) 1997-06-10 1999-10-26 Th. Goldschmidt Ag Foamable metal articles
US5981812A (en) 1996-11-25 1999-11-09 Th. Goldschmidt Ag Process for preparing α, ω-alkenols
US6197089B1 (en) 1999-02-24 2001-03-06 Goldschmidt, A.G Activated magnesium metal
US6255511B1 (en) 1993-09-06 2001-07-03 Th Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US6291622B1 (en) 1998-12-23 2001-09-18 Goldschmidt Ag Process and apparatus for continuous hydrosilylation
US6307082B1 (en) 1999-02-24 2001-10-23 Goldschmidt Ag Synergistic catalyst system and process for carrying out hydrosilylation reactions
US6387154B1 (en) 1999-02-24 2002-05-14 Th. Goldschmidt Ag Process for separating molten metals
WO2002060621A2 (de) 2001-02-01 2002-08-08 Goldschmidt Ag Verfahren zur herstellung von metallschaum und danach hergestellter metallkörper
US6444007B1 (en) 1999-02-24 2002-09-03 Goldschmidt Ag Production of metal foams
US20020161158A1 (en) 2001-02-27 2002-10-31 Georg Burkhart Process for working-up polyethersiloxanes
US6521771B2 (en) 2000-05-19 2003-02-18 Goldschmidt Ag Use of zinc treated with metal hydride in organometallic synthesis
EP1350804A1 (de) 2002-03-26 2003-10-08 Goldschmidt AG Verwendung organofunktionell modifizierter Polysiloxane zur Herstellung von Polyurethanweichschäumen
US6659162B2 (en) 2001-02-01 2003-12-09 Goldschmidt Ag Production of large-area metallic integral foams
US6854506B2 (en) 2001-05-16 2005-02-15 Goldschmidt Ag Process for producing shaped metal parts
US6858663B2 (en) 2002-07-16 2005-02-22 Goldschmidt Ag Organopolysiloxanes for defoaming aqueous systems
US6874562B2 (en) 2001-06-07 2005-04-05 Goldschmidt Ag Process for producing metal/metal foam composite components
US6915834B2 (en) 2001-02-01 2005-07-12 Goldschmidt Ag Process for producing metal foam and metal body produced using this process
US6942716B2 (en) 2001-05-19 2005-09-13 Goldschmidt Gmbh Production of metal forms
US7018458B2 (en) 2002-07-19 2006-03-28 Goldschmidt Gmbh Use of organofunctionally modified polysiloxanes containing phenyl derivatives as dispersants and wetting agents for fillers and pigments in aqueous pigment pastes and ink or paint formulations
US7125585B2 (en) 2002-09-26 2006-10-24 Goldschmidt Gmbh Siloxane compounds and their use as homogenizer in release agents with matting effect for producing moldings from plastics with matt surfaces
US7157541B2 (en) 2003-10-04 2007-01-02 Goldschmidt Gmbh Process for an addition reaction of organic silicon compounds having SiH groups with compounds having olefinic double bonds
US7196153B2 (en) 2003-01-16 2007-03-27 Goldschmidt Ag Equilibration of siloxanes
US20070128143A1 (en) 2005-12-03 2007-06-07 Goldschmidt Gmbh Polyether-modified polysiloxanes with block character and use thereof for producing cosmetic formulations
US20090137752A1 (en) 2007-11-28 2009-05-28 Evonik Goldschmidt Gmbh Process for preparing polyether alcohols with DMC catalysts using specific additives with aromatic hydroxyl functionalization
US7598334B2 (en) 2005-01-07 2009-10-06 Goldschmidt Gmbh Process for preparing equilibration products of organosiloxanes, the organopolysiloxanes thus obtainable, and use thereof
US7612159B2 (en) 2002-12-21 2009-11-03 Goldschmidt Ag Process for working up polyethersiloxanes
US7619035B2 (en) 2005-08-20 2009-11-17 Goldschmidt Gmbh Method of producing addition products of compounds containing SiH groups onto reactants having one double bond on aqueous media
US7645848B2 (en) 2005-08-24 2010-01-12 Goldschmidt Gmbh Process for preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers
US20100081781A1 (en) 2008-04-01 2010-04-01 Frank Schubert Novel polyether alcohols which bear organosiloxane groups through alkoxylation of epoxy-functional (poly)organosiloxanes over double metal cyanide (dmc) catalysts and processes for preparation thereof
US7754778B2 (en) 2007-07-27 2010-07-13 Evonik Goldschmidt Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers linked via Si-C groups and via carboxylic ester groups, a process for preparing them and their use
US7825205B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for the preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers and their use
US7825209B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for the preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers and their use
US7825206B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for reacting polyorganosiloxanes and their use
US20110230619A1 (en) 2010-02-22 2011-09-22 Evonik Goldschmidt Gmbh Nitrogen-Containing Organosilicon Graft Copolymers
US20110301254A1 (en) 2010-06-07 2011-12-08 Evonik Goldschmidt Gmbh Process for preparing organic silicon compounds
US8138294B2 (en) 2008-08-27 2012-03-20 Evonik Goldschmidt Gmbh Process for preparing branched Si-H functional polysiloxanes and use thereof for preparing liquid SiC- or SiOC-linked, branched modified organomodified polysiloxanes
US20120068110A1 (en) 2009-05-25 2012-03-22 Evonik Goldschmidt Gmbh Hydroxyl Compounds Carrying Reactive Silyl Groups And Used As Ceramic Binders
US8247525B2 (en) 2010-02-03 2012-08-21 Evonik Goldschmidt Gmbh Particles and composite particles, their uses and a novel process for producing them from alkoxysilyl-group-carrying alkoxylation products
US8268939B2 (en) 2008-12-05 2012-09-18 Evonik Goldschmidt Gmbh Process for modifying surfaces
US8283422B2 (en) 2008-12-05 2012-10-09 Evonik Goldschmidt Gmbh Polyethersiloxanes carrying alkoxysilyl groups and method for production thereof
US20120282210A1 (en) 2010-02-03 2012-11-08 Evonik Goldschmidt Gmbh Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof
US8309673B2 (en) 2008-06-27 2012-11-13 Evonik Goldschmidt Gmbh Polyether siloxane-containing alkoxylation products by direct alkoxylation of organomodified α,ω-dihydroxysiloxanes over double metal cyanide (DMC) catalysts, and also process for producing them
US8309664B2 (en) 2008-10-29 2012-11-13 Evonik Goldschmidt Gmbh Silicone-polyether copolymer systems and process for preparing them by means of an alkoxylation reaction
US8324325B2 (en) 2007-11-28 2012-12-04 Evonik Goldschmidt Gmbh Process for preparing polyether alcohols with DMC catalysts using compounds bearing SiH groups as additives
US8334355B2 (en) 2008-10-31 2012-12-18 Evonik Goldschmidt Gmbh Silicone-polyether block copolymers having a defined polydispersity in the polyoxyalkylene part and their use as stabilizers for producing polyurethane foams
US8349907B2 (en) 2008-02-11 2013-01-08 Evonik Goldschmidt Gmbh Invention relates to the use of foam stabilizers, produced on the basis of sustainable raw materials, for prroducing polyurethane foams
WO2013010747A1 (de) 2011-07-20 2013-01-24 Evonik Goldschmidt Gmbh Verfahren zur reduktion von carbonsäureestern oder -lactonen zu den entsprechenden ethern
US8450514B2 (en) 2008-02-21 2013-05-28 Evonik Goldschmidt Gmbh Polyether alcohols bearing alkoxysilyl groups by alkoxylation of epoxy-functional alkoxysilances over double metal cyanide (DMC) catalysts, and processes for preparation thereof
US8455603B2 (en) 2010-02-22 2013-06-04 Evonik Goldschmidt Gmbh Process for the preparation of amine-amide-functional siloxanes
US20130213267A1 (en) 2012-02-20 2013-08-22 Evonik Goldschmidt Gmbh Composition Comprising Polymers and Metal Atoms or Ions and Use Thereof
US8557944B2 (en) 2010-10-25 2013-10-15 Evonik Goldschmidt Gmbh Polysiloxanes with nitrogen-containing groups
US8598295B2 (en) 2007-11-21 2013-12-03 Evonik Goldschmidt Gmbh Method for producing branched SiH functional polysiloxanes and the use thereof for producing SiC- and SiOC-linked, branched organomodified polysiloxanes
US8609798B2 (en) 2007-11-21 2013-12-17 Evonik Goldschmidt Gmbh Process for preparing polydimethylsiloxanes on sulphonic acid cation exchange resins
US20130345318A1 (en) 2012-06-22 2013-12-26 Evonik Industries Ag Silicone polyethers and preparation thereof from polyethers bearing methylidene groups
US8722836B2 (en) 2011-12-16 2014-05-13 Evonik Industries Ag Siloxane nitrones and use thereof
US8722834B2 (en) 2008-09-18 2014-05-13 Evonik Goldschmidt Gmbh Equilibration of siloxanes on water-containing sulphonated cation exchange resins
US8729207B2 (en) 2010-07-08 2014-05-20 Evonik Degussa Gmbh Types of polyester-modified organopolysiloxanes
US8772423B2 (en) 2009-05-25 2014-07-08 Evonik Degussa Gmbh Emulsions based on hydroxyl compounds bearing silyl groups
US8779079B2 (en) 2009-07-24 2014-07-15 Evonik Degussa Gmbh Silicone polyether copolymers and process for preparation thereof
US8802744B2 (en) 2011-08-03 2014-08-12 Evonik Degussa Gmbh Alkyl carbonate endcapped polyether siloxanes and preparation thereof
US8841400B2 (en) 2009-04-16 2014-09-23 Evonik Degussa Gmbh Use of organomodified siloxanes branched in the silicone part for producing cosmetic or pharmaceutical compositions
US20140309446A1 (en) 2011-10-31 2014-10-16 Evonik Degussa Gmbh Novel amino-group-containing siloxanes, processes for their preparation and use
US8921437B2 (en) 2008-09-24 2014-12-30 Evonik Goldschmidt Gmbh Polymeric materials and also adhesive and coating compositions composed thereof and based on multi-alkoxysilyl-functional prepolymers
US20150004112A1 (en) 2013-07-01 2015-01-01 Evonik Industries Ag Siloxane polymers with a central polysiloxane polymer block with organofunctional radicals each having at least two bivalent groups selected from urea and/or carbamate groups and at least one uv/vis chromophore as radical
US20150004113A1 (en) 2013-07-01 2015-01-01 Evonik Industries Ag Siloxane polymers with a central polysiloxane polymer block with terminal organofunctional radicals comprising urea and/or carbamate groups and amino acid radicals
US8946369B2 (en) 2012-02-20 2015-02-03 Evonik Degussa Gmbh Branched polysiloxanes and use of these
US8957009B2 (en) 2010-01-29 2015-02-17 Evonik Degussa Gmbh Linear polydimethylsiloxane-polyether copolymers having amino and/or quaternary ammonium groups and use thereof
US8974627B2 (en) 2009-05-25 2015-03-10 Evonik Degussa Gmbh Curable compositions containing silyl groups, and use thereof
US8993706B2 (en) 2009-08-19 2015-03-31 Evonik Degussa Gmbh Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants, adhesives, binders and/or surface modifiers
US9035011B2 (en) 2012-03-09 2015-05-19 Evonik Goldschmidt Gmbh Modified alkoxylation products having at least one non-terminal alkoxysilyl group and a plurality of urethane groups, and their use
US9068044B2 (en) 2011-05-18 2015-06-30 Evonik Degussa Gmbh Alkoxylation products and process for preparing them by means of DMC catalysts
US9315614B2 (en) 2009-08-19 2016-04-19 Evonik Degussa Gmbh Urethane-containing silylated prepolymers and process for preparation thereof
US9334354B2 (en) 2013-08-23 2016-05-10 Evonik Degussa Gmbh Modified alkoxylation products which have alkoxysilyl groups and contain urethane groups, and their use
US20160130290A1 (en) 2014-11-12 2016-05-12 Evonik Degussa Gmbh Process for producing compositions comprising platinum
US20160130402A1 (en) 2013-07-12 2016-05-12 Evonik Degussa Gmbh Curable compositions containing silyl groups and having improved storage stability
US9353225B2 (en) 2013-08-23 2016-05-31 Evonik Degussa Gmbh Compounds having guanidine groups and containing semi-organic silicon groups
US20160160009A1 (en) 2014-12-05 2016-06-09 Evonik Degussa Gmbh Production of polyether siloxanes
US9481695B2 (en) 2013-07-18 2016-11-01 Evonik Industries Ag Amino acid-modified siloxanes, process for preparing them and application
US20170081469A1 (en) 2014-05-19 2017-03-23 Evonik Degussa-GmbH Ethoxylate production using highly active double metal cyanide catalysts
WO2017080747A1 (de) 2015-11-11 2017-05-18 Evonik Degussa Gmbh Härtbare polymere
WO2017089068A1 (de) 2015-11-26 2017-06-01 Evonik Degussa Gmbh Bindemittelsysteme enthaltend alkoxysilylgruppen tragende präpolymere und epoxidverbindungen sowie deren verwendung
US20170198099A1 (en) 2014-07-11 2017-07-13 Evonik Degussa Gmbh Composition containing platinum
US20170226285A1 (en) 2016-02-04 2017-08-10 Evonik Degussa Gmbh Alkoxysilyl-containing adhesive sealants having improved tear propagation resistance
US9783635B2 (en) 2013-05-07 2017-10-10 Evonik Degussa Gmbh Polyoxyalkylenes with pendant long-chain acyloxy groups and method for producing same using DMC catalysts
WO2017174272A1 (de) 2016-04-04 2017-10-12 Evonik Degussa Gmbh Aufbereitung alkalisch katalysierter alkoxylierungsprodukte
US20180016392A1 (en) 2015-01-28 2018-01-18 Evonik Degussa Gmbh Modified alkoxylation products having at least one non-terminal alkoxy silyl group, with increased storage stability and improved elongation, and the polymers produced using said products
WO2018015152A1 (de) 2016-07-22 2018-01-25 Evonik Degussa Gmbh Verfahren zur herstellung von siloxanen enthaltend glycerinsubstituenten
US9896541B2 (en) 2014-05-19 2018-02-20 Evonik Degussa Gmbh Highly active double metal cyanide catalysts and method for the production thereof
EP3321304A1 (de) 2016-11-15 2018-05-16 Evonik Degussa GmbH Mischungen zyklischer-verzweigter siloxane vom d/t-typ und deren folgeprodukte
US20180258228A1 (en) 2015-11-11 2018-09-13 Evonik Degussa Gmbh Curable polymers

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2758124A (en) 1952-04-11 1956-08-07 Gen Electric Continuous hydrolysis of organohalogenosilanes
DE1125180B (de) 1959-07-21 1962-03-08 Goldschmidt Ag Th Verfahren zur Hydrolyse von Chlorsilanen mit unmittelbar an Silicium gebundenem Wasserstoff bzw. organofunktionellen Gruppen
DE2453482B2 (de) * 1974-11-12 1980-04-30 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von endständig chlorsubstituierten, linearen oder verzweigten Organosiloxanen
GB8428401D0 (en) 1984-11-09 1984-12-19 Dow Corning Ltd Organosiloxane-oxy-alkylene copolymers
DE3716372A1 (de) 1987-05-15 1988-11-24 Wacker Chemie Gmbh Verfahren zur herstellung von organopolysiloxanen und ein neues organopolysiloxan
GB8902179D0 (en) 1989-02-01 1989-03-22 Dow Corning Conditioning compositions
DE4411079A1 (de) 1994-03-30 1995-10-05 Bayer Ag Neuartige Copolymere auf verzweigter Polysiloxan-Polyether-Basis, ein Verfahren zu ihrer Herstellung und ihre Verwendung
US6730749B1 (en) 1997-03-29 2004-05-04 Goldschmidt Ag Siloxane block copolymers having linked siloxane blocks
DE19828390A1 (de) 1998-06-25 1999-12-30 Wacker Chemie Gmbh Verfahren zur Herstellung von Hydrogenmethylpolysiloxanen mit Trimethylsilyl-Endgruppen
JP4949550B2 (ja) 2000-12-11 2012-06-13 信越化学工業株式会社 化粧料
US7211638B2 (en) * 2003-06-25 2007-05-01 Intel Corporation Silicone-based cyanate-ester cross-linkable die attach adhesive
DE102005004676A1 (de) 2005-02-02 2006-08-10 Goldschmidt Gmbh Lösungsmittelfreies Verfahren zur Umsetzung von verzweigten Polyorganosiloxanen
DE102005018629A1 (de) 2005-04-21 2006-10-26 Wacker Chemie Ag Verfahren zur Herstellung von Triorganosiloxygruppen aufweisenden Organopolysiloxanen
DE102005030579A1 (de) * 2005-06-30 2007-01-04 Wacker Chemie Ag Siliconharze mit definierter Reaktivität
JP5306220B2 (ja) * 2006-11-29 2013-10-02 ダウ・コーニング・コーポレイション シリコーン樹脂の水性エマルジョン
CN102089396A (zh) * 2008-05-28 2011-06-08 陶氏康宁公司 涂料组合物
JP5577081B2 (ja) * 2009-12-03 2014-08-20 東レ・ダウコーニング株式会社 新規オルガノポリシロキサン及び化粧料
JP5698836B2 (ja) * 2010-05-20 2015-04-08 ダウ コーニング コーポレーションＤｏｗ Ｃｏｒｎｉｎｇ Ｃｏｒｐｏｒａｔｉｏｎ シリコーン樹脂及びそのポリマー組成物への使用
JP6369888B2 (ja) * 2011-12-27 2018-08-08 東レ・ダウコーニング株式会社 新規液状オルガノポリシロキサン及びその利用
JP5819866B2 (ja) * 2013-01-10 2015-11-24 信越化学工業株式会社 付加硬化型シリコーン組成物、光学素子封止材および光学素子
JP6329764B2 (ja) * 2013-03-15 2018-05-23 信越化学工業株式会社 対称ハイパーブランチ型シリコーン変性重合性化合物、及びそのモジュール化した製造方法
CN106536634B (zh) * 2014-07-23 2020-03-17 美国陶氏有机硅公司 粘液性有机硅流体

Patent Citations (117)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5093101A (en) 1990-09-04 1992-03-03 Th. Goldschmidt Ag Method for the preparation of active magnesium hydride-magnesium-hydrogen storage systems and apparatus for carrying out the method
US5198207A (en) 1990-12-08 1993-03-30 Th. Goldschmidt Ag Method for the preparation of active magnesium hydride-magnesium hydrogen storage systems, which reversibly absorb hydrogen
US5221499A (en) 1991-05-18 1993-06-22 Th. Goldschmidt Ag Method for the preparation of dialkylmagnesium compounds by the reaction of magnesium hydride with an olefin
EP0514737A1 (de) 1991-05-24 1992-11-25 Th. Goldschmidt AG Verfahren zur Herstellung von Organopolysiloxanen mit mindestens einer an ein Si-Atom gebundenen Cyclopentadienylgruppe
US5831103A (en) 1992-10-20 1998-11-03 Th. Goldschmidt Ag Halogen-magnesium-aluminum hydridohalides, methods for their synthesis and their use as reducing agents
US5371161A (en) 1992-11-21 1994-12-06 Th. Goldschmidt Ag Method for the preparation of organopolysiloxanes containing SIH groups
US5455367A (en) 1993-04-22 1995-10-03 Th. Goldschmidt Ag Method for the synthesis of silanes or organosilicon hydrides by the reduction of the corresponding silicon halides or organosilicon halides
US5430166A (en) 1993-06-24 1995-07-04 Th. Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US5430167A (en) 1993-06-24 1995-07-04 Th. Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US6489498B2 (en) 1993-09-06 2002-12-03 Th. Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US6255511B1 (en) 1993-09-06 2001-07-03 Th Goldschmidt Ag Silanes with hydrophilic groups, their synthesis and use as surfactants in aqueous media
US5565183A (en) 1993-10-27 1996-10-15 Th. Goldschmidt Ag Method for the preparation of aluminum hydride (AlH3) by reacting magnesium hydride with aluminum halide
US5475127A (en) 1994-04-27 1995-12-12 Th. Goldschmidt Ag Organosilyl and organosiloxanyl derivatives of glycerin ethers and their use
EP0685425A1 (de) 1994-06-03 1995-12-06 Th. Goldschmidt AG Verfahren zur Herstellung von Magnesium-hydrid
US5670129A (en) 1994-12-24 1997-09-23 Th. Goldschmidt Ag. Method for synthesizing aluminum hydride
US5951739A (en) 1995-05-26 1999-09-14 Th. Goldschmidt Ag Process for preparing x-ray amorphous and nanocrystalline metal powders
US5934579A (en) 1996-04-03 1999-08-10 Th. Goldschmidt Ag Apparatus for treating suspensions
US5981812A (en) 1996-11-25 1999-11-09 Th. Goldschmidt Ag Process for preparing α, ω-alkenols
US5856548A (en) 1997-05-17 1999-01-05 Th. Goldschmidt Ag Process for preparing dimethylmonochlorosilane
US5972285A (en) 1997-06-10 1999-10-26 Th. Goldschmidt Ag Foamable metal articles
US6291622B1 (en) 1998-12-23 2001-09-18 Goldschmidt Ag Process and apparatus for continuous hydrosilylation
US6307082B1 (en) 1999-02-24 2001-10-23 Goldschmidt Ag Synergistic catalyst system and process for carrying out hydrosilylation reactions
US6387154B1 (en) 1999-02-24 2002-05-14 Th. Goldschmidt Ag Process for separating molten metals
US6444007B1 (en) 1999-02-24 2002-09-03 Goldschmidt Ag Production of metal foams
US6197089B1 (en) 1999-02-24 2001-03-06 Goldschmidt, A.G Activated magnesium metal
US6521771B2 (en) 2000-05-19 2003-02-18 Goldschmidt Ag Use of zinc treated with metal hydride in organometallic synthesis
WO2002060621A2 (de) 2001-02-01 2002-08-08 Goldschmidt Ag Verfahren zur herstellung von metallschaum und danach hergestellter metallkörper
US6915834B2 (en) 2001-02-01 2005-07-12 Goldschmidt Ag Process for producing metal foam and metal body produced using this process
US6659162B2 (en) 2001-02-01 2003-12-09 Goldschmidt Ag Production of large-area metallic integral foams
US20020161158A1 (en) 2001-02-27 2002-10-31 Georg Burkhart Process for working-up polyethersiloxanes
US6854506B2 (en) 2001-05-16 2005-02-15 Goldschmidt Ag Process for producing shaped metal parts
US6942716B2 (en) 2001-05-19 2005-09-13 Goldschmidt Gmbh Production of metal forms
US6874562B2 (en) 2001-06-07 2005-04-05 Goldschmidt Ag Process for producing metal/metal foam composite components
EP1350804A1 (de) 2002-03-26 2003-10-08 Goldschmidt AG Verwendung organofunktionell modifizierter Polysiloxane zur Herstellung von Polyurethanweichschäumen
US6858663B2 (en) 2002-07-16 2005-02-22 Goldschmidt Ag Organopolysiloxanes for defoaming aqueous systems
US7018458B2 (en) 2002-07-19 2006-03-28 Goldschmidt Gmbh Use of organofunctionally modified polysiloxanes containing phenyl derivatives as dispersants and wetting agents for fillers and pigments in aqueous pigment pastes and ink or paint formulations
US7125585B2 (en) 2002-09-26 2006-10-24 Goldschmidt Gmbh Siloxane compounds and their use as homogenizer in release agents with matting effect for producing moldings from plastics with matt surfaces
US7612159B2 (en) 2002-12-21 2009-11-03 Goldschmidt Ag Process for working up polyethersiloxanes
US7196153B2 (en) 2003-01-16 2007-03-27 Goldschmidt Ag Equilibration of siloxanes
US7612158B2 (en) 2003-01-16 2009-11-03 Goldschmidt Ag Equilibration of siloxanes
US7157541B2 (en) 2003-10-04 2007-01-02 Goldschmidt Gmbh Process for an addition reaction of organic silicon compounds having SiH groups with compounds having olefinic double bonds
US7598334B2 (en) 2005-01-07 2009-10-06 Goldschmidt Gmbh Process for preparing equilibration products of organosiloxanes, the organopolysiloxanes thus obtainable, and use thereof
US20100022435A1 (en) 2005-08-20 2010-01-28 Goldschmidt Gmbh METHOD OF PRODUCING ADDITION PRODUCTS OF COMPOUNDS CONTAINING SiH GROUPS ONTO REACTANTS HAVING ONE DOUBLE BOND IN AQUEOUS MEDIA
US7619035B2 (en) 2005-08-20 2009-11-17 Goldschmidt Gmbh Method of producing addition products of compounds containing SiH groups onto reactants having one double bond on aqueous media
US7645848B2 (en) 2005-08-24 2010-01-12 Goldschmidt Gmbh Process for preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers
US20070128143A1 (en) 2005-12-03 2007-06-07 Goldschmidt Gmbh Polyether-modified polysiloxanes with block character and use thereof for producing cosmetic formulations
US7825205B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for the preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers and their use
US7825209B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for the preparation of SiOC-linked, linear polydimethylsiloxane-polyoxyalkylene block copolymers and their use
US7825206B2 (en) 2006-12-22 2010-11-02 Evonik Goldschmidt Gmbh Process for reacting polyorganosiloxanes and their use
US7754778B2 (en) 2007-07-27 2010-07-13 Evonik Goldschmidt Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers linked via Si-C groups and via carboxylic ester groups, a process for preparing them and their use
US8969502B2 (en) 2007-11-21 2015-03-03 Evonik Degussa Gmbh Process for preparing polydimethylsiloxanes on sulphonic acid cation exchange resins
US8598295B2 (en) 2007-11-21 2013-12-03 Evonik Goldschmidt Gmbh Method for producing branched SiH functional polysiloxanes and the use thereof for producing SiC- and SiOC-linked, branched organomodified polysiloxanes
US8609798B2 (en) 2007-11-21 2013-12-17 Evonik Goldschmidt Gmbh Process for preparing polydimethylsiloxanes on sulphonic acid cation exchange resins
US8324325B2 (en) 2007-11-28 2012-12-04 Evonik Goldschmidt Gmbh Process for preparing polyether alcohols with DMC catalysts using compounds bearing SiH groups as additives
US20090137752A1 (en) 2007-11-28 2009-05-28 Evonik Goldschmidt Gmbh Process for preparing polyether alcohols with DMC catalysts using specific additives with aromatic hydroxyl functionalization
US8349907B2 (en) 2008-02-11 2013-01-08 Evonik Goldschmidt Gmbh Invention relates to the use of foam stabilizers, produced on the basis of sustainable raw materials, for prroducing polyurethane foams
US8450514B2 (en) 2008-02-21 2013-05-28 Evonik Goldschmidt Gmbh Polyether alcohols bearing alkoxysilyl groups by alkoxylation of epoxy-functional alkoxysilances over double metal cyanide (DMC) catalysts, and processes for preparation thereof
US9975909B2 (en) 2008-02-21 2018-05-22 Evonik Degussa Gmbh Polyether alcohols bearing alkoxysilyl groups by alkoxylation of epoxy-functional alkoxysilanes over double metal cyanide (DMC) catalysts, and processes for preparation thereof
US20100081781A1 (en) 2008-04-01 2010-04-01 Frank Schubert Novel polyether alcohols which bear organosiloxane groups through alkoxylation of epoxy-functional (poly)organosiloxanes over double metal cyanide (dmc) catalysts and processes for preparation thereof
US8309673B2 (en) 2008-06-27 2012-11-13 Evonik Goldschmidt Gmbh Polyether siloxane-containing alkoxylation products by direct alkoxylation of organomodified α,ω-dihydroxysiloxanes over double metal cyanide (DMC) catalysts, and also process for producing them
US8138294B2 (en) 2008-08-27 2012-03-20 Evonik Goldschmidt Gmbh Process for preparing branched Si-H functional polysiloxanes and use thereof for preparing liquid SiC- or SiOC-linked, branched modified organomodified polysiloxanes
US8420748B2 (en) 2008-08-27 2013-04-16 Evonik Goldschmidt Gmbh Process for preparing branched Si-H functional polysiloxanes and use thereof for preparing liquid SiC- or SiOC-linked, branched modified organomodified polysiloxanes
US8722834B2 (en) 2008-09-18 2014-05-13 Evonik Goldschmidt Gmbh Equilibration of siloxanes on water-containing sulphonated cation exchange resins
US8921437B2 (en) 2008-09-24 2014-12-30 Evonik Goldschmidt Gmbh Polymeric materials and also adhesive and coating compositions composed thereof and based on multi-alkoxysilyl-functional prepolymers
US8309664B2 (en) 2008-10-29 2012-11-13 Evonik Goldschmidt Gmbh Silicone-polyether copolymer systems and process for preparing them by means of an alkoxylation reaction
US20130041115A1 (en) 2008-10-29 2013-02-14 Evonik Goldschmidt Gmbh Silicone-polyether copolymer systems and process for preparing them by means of an alkoxylation reaction
US8334355B2 (en) 2008-10-31 2012-12-18 Evonik Goldschmidt Gmbh Silicone-polyether block copolymers having a defined polydispersity in the polyoxyalkylene part and their use as stabilizers for producing polyurethane foams
US8283422B2 (en) 2008-12-05 2012-10-09 Evonik Goldschmidt Gmbh Polyethersiloxanes carrying alkoxysilyl groups and method for production thereof
US8268939B2 (en) 2008-12-05 2012-09-18 Evonik Goldschmidt Gmbh Process for modifying surfaces
US8841400B2 (en) 2009-04-16 2014-09-23 Evonik Degussa Gmbh Use of organomodified siloxanes branched in the silicone part for producing cosmetic or pharmaceutical compositions
US8772423B2 (en) 2009-05-25 2014-07-08 Evonik Degussa Gmbh Emulsions based on hydroxyl compounds bearing silyl groups
US8974627B2 (en) 2009-05-25 2015-03-10 Evonik Degussa Gmbh Curable compositions containing silyl groups, and use thereof
US20120068110A1 (en) 2009-05-25 2012-03-22 Evonik Goldschmidt Gmbh Hydroxyl Compounds Carrying Reactive Silyl Groups And Used As Ceramic Binders
US20140256844A1 (en) 2009-07-24 2014-09-11 Evonik Degussa Gmbh Novel silicone polyether copolymers and process for preparation thereof
US8779079B2 (en) 2009-07-24 2014-07-15 Evonik Degussa Gmbh Silicone polyether copolymers and process for preparation thereof
US8993706B2 (en) 2009-08-19 2015-03-31 Evonik Degussa Gmbh Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants, adhesives, binders and/or surface modifiers
US9315614B2 (en) 2009-08-19 2016-04-19 Evonik Degussa Gmbh Urethane-containing silylated prepolymers and process for preparation thereof
US9441145B2 (en) 2009-08-19 2016-09-13 Evonik Degussa Gmbh Curable material comprising silylated polymers containing urethane groups, and use thereof in sealants, adhesives, binders and/or surface modifiers
US8957009B2 (en) 2010-01-29 2015-02-17 Evonik Degussa Gmbh Linear polydimethylsiloxane-polyether copolymers having amino and/or quaternary ammonium groups and use thereof
US9695202B2 (en) 2010-02-03 2017-07-04 Evonik Degussa Gmbh Organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof
US8247525B2 (en) 2010-02-03 2012-08-21 Evonik Goldschmidt Gmbh Particles and composite particles, their uses and a novel process for producing them from alkoxysilyl-group-carrying alkoxylation products
US20120282210A1 (en) 2010-02-03 2012-11-08 Evonik Goldschmidt Gmbh Novel organomodified siloxanes having primary amino functions, novel organomodified siloxanes having quaternary ammonium functions and the method for the production thereof
US20110230619A1 (en) 2010-02-22 2011-09-22 Evonik Goldschmidt Gmbh Nitrogen-Containing Organosilicon Graft Copolymers
US8455603B2 (en) 2010-02-22 2013-06-04 Evonik Goldschmidt Gmbh Process for the preparation of amine-amide-functional siloxanes
US20110301254A1 (en) 2010-06-07 2011-12-08 Evonik Goldschmidt Gmbh Process for preparing organic silicon compounds
US8729207B2 (en) 2010-07-08 2014-05-20 Evonik Degussa Gmbh Types of polyester-modified organopolysiloxanes
US8557944B2 (en) 2010-10-25 2013-10-15 Evonik Goldschmidt Gmbh Polysiloxanes with nitrogen-containing groups
US9068044B2 (en) 2011-05-18 2015-06-30 Evonik Degussa Gmbh Alkoxylation products and process for preparing them by means of DMC catalysts
WO2013010747A1 (de) 2011-07-20 2013-01-24 Evonik Goldschmidt Gmbh Verfahren zur reduktion von carbonsäureestern oder -lactonen zu den entsprechenden ethern
US8802744B2 (en) 2011-08-03 2014-08-12 Evonik Degussa Gmbh Alkyl carbonate endcapped polyether siloxanes and preparation thereof
US20140309446A1 (en) 2011-10-31 2014-10-16 Evonik Degussa Gmbh Novel amino-group-containing siloxanes, processes for their preparation and use
US8722836B2 (en) 2011-12-16 2014-05-13 Evonik Industries Ag Siloxane nitrones and use thereof
US8946369B2 (en) 2012-02-20 2015-02-03 Evonik Degussa Gmbh Branched polysiloxanes and use of these
US20130213267A1 (en) 2012-02-20 2013-08-22 Evonik Goldschmidt Gmbh Composition Comprising Polymers and Metal Atoms or Ions and Use Thereof
US9035011B2 (en) 2012-03-09 2015-05-19 Evonik Goldschmidt Gmbh Modified alkoxylation products having at least one non-terminal alkoxysilyl group and a plurality of urethane groups, and their use
US20130345318A1 (en) 2012-06-22 2013-12-26 Evonik Industries Ag Silicone polyethers and preparation thereof from polyethers bearing methylidene groups
US9783635B2 (en) 2013-05-07 2017-10-10 Evonik Degussa Gmbh Polyoxyalkylenes with pendant long-chain acyloxy groups and method for producing same using DMC catalysts
US20150004112A1 (en) 2013-07-01 2015-01-01 Evonik Industries Ag Siloxane polymers with a central polysiloxane polymer block with organofunctional radicals each having at least two bivalent groups selected from urea and/or carbamate groups and at least one uv/vis chromophore as radical
US20150004113A1 (en) 2013-07-01 2015-01-01 Evonik Industries Ag Siloxane polymers with a central polysiloxane polymer block with terminal organofunctional radicals comprising urea and/or carbamate groups and amino acid radicals
US20160130402A1 (en) 2013-07-12 2016-05-12 Evonik Degussa Gmbh Curable compositions containing silyl groups and having improved storage stability
US9481695B2 (en) 2013-07-18 2016-11-01 Evonik Industries Ag Amino acid-modified siloxanes, process for preparing them and application
US9334354B2 (en) 2013-08-23 2016-05-10 Evonik Degussa Gmbh Modified alkoxylation products which have alkoxysilyl groups and contain urethane groups, and their use
US9353225B2 (en) 2013-08-23 2016-05-31 Evonik Degussa Gmbh Compounds having guanidine groups and containing semi-organic silicon groups
US9896541B2 (en) 2014-05-19 2018-02-20 Evonik Degussa Gmbh Highly active double metal cyanide catalysts and method for the production thereof
US20170081469A1 (en) 2014-05-19 2017-03-23 Evonik Degussa-GmbH Ethoxylate production using highly active double metal cyanide catalysts
US20170198099A1 (en) 2014-07-11 2017-07-13 Evonik Degussa Gmbh Composition containing platinum
US20160130290A1 (en) 2014-11-12 2016-05-12 Evonik Degussa Gmbh Process for producing compositions comprising platinum
US20160160009A1 (en) 2014-12-05 2016-06-09 Evonik Degussa Gmbh Production of polyether siloxanes
US20180016392A1 (en) 2015-01-28 2018-01-18 Evonik Degussa Gmbh Modified alkoxylation products having at least one non-terminal alkoxy silyl group, with increased storage stability and improved elongation, and the polymers produced using said products
WO2017080747A1 (de) 2015-11-11 2017-05-18 Evonik Degussa Gmbh Härtbare polymere
US20180258228A1 (en) 2015-11-11 2018-09-13 Evonik Degussa Gmbh Curable polymers
WO2017089068A1 (de) 2015-11-26 2017-06-01 Evonik Degussa Gmbh Bindemittelsysteme enthaltend alkoxysilylgruppen tragende präpolymere und epoxidverbindungen sowie deren verwendung
US20170226285A1 (en) 2016-02-04 2017-08-10 Evonik Degussa Gmbh Alkoxysilyl-containing adhesive sealants having improved tear propagation resistance
WO2017174272A1 (de) 2016-04-04 2017-10-12 Evonik Degussa Gmbh Aufbereitung alkalisch katalysierter alkoxylierungsprodukte
WO2018015152A1 (de) 2016-07-22 2018-01-25 Evonik Degussa Gmbh Verfahren zur herstellung von siloxanen enthaltend glycerinsubstituenten
EP3321304A1 (de) 2016-11-15 2018-05-16 Evonik Degussa GmbH Mischungen zyklischer-verzweigter siloxane vom d/t-typ und deren folgeprodukte
US20180134850A1 (en) 2016-11-15 2018-05-17 Evonik Degussa Gmbh Mixtures of cyclic branched siloxanes of the d/t type and conversion products thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Nam et al., "Condensation reaction of 3-(methacryloxypropyl)-trimethoxysilane and diisobutylsilanediol in non-hydrolytic sol-gel process," copyright 2006, J. Sol-Gel Sci. Techn., vol. 39, pp. 255-260 (7 pages).

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11345783B2 (en) 2018-05-17 2022-05-31 Evonik Operations Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers of the structure type ABA
US11359056B2 (en) 2018-05-17 2022-06-14 Evonik Operations Gmbh Linear polydimethylsiloxane-polyoxyalkylene block copolymers of the structure type ABA
US11795275B2 (en) 2018-12-04 2023-10-24 Evonik Operations Gmbh Reactive siloxanes
US11286366B2 (en) 2019-05-28 2022-03-29 Evonik Operations Gmbh Process for recycling silicones
US11498996B2 (en) 2019-05-28 2022-11-15 Evonik Operations Gmbh Process for producing polyoxyalkylene polysiloxane block polymers
US11859053B2 (en) 2020-02-14 2024-01-02 Evonik Operations Gmbh SiOC-bonded, linear polydimethylsiloxane-polyoxyalkylene block copolymers
US11591448B2 (en) 2020-03-27 2023-02-28 Evonik Operations Gmbh Physical reutilization of siliconized sheets
US11732092B2 (en) 2020-10-19 2023-08-22 Evonik Operations Gmbh Upcycling process for processing silicone wastes
US12152109B2 (en) 2020-12-09 2024-11-26 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes
US12060460B2 (en) 2021-04-29 2024-08-13 Evonik Operations Gmbh Process for producing endcapped, liquid siloxanes from silicone wastes
US12577351B2 (en) 2021-07-14 2026-03-17 Evonik Operations Gmbh Increasing the molecular weight of low molecular weight alpha,omega-polysiloxanediols
US12460081B2 (en) 2021-11-25 2025-11-04 Evonik Operations Gmbh Curable condensation compounds based on alkoxy-functional polysiloxanes

Also Published As

Publication number Publication date
CN109627444A (zh) 2019-04-16
US20190106441A1 (en) 2019-04-11
EP3467006B1 (de) 2022-11-30
CA3020081A1 (en) 2019-04-09
EP3467006A1 (de) 2019-04-10
CN109627444B (zh) 2022-06-28

Similar Documents

Publication Publication Date Title
US10766913B2 (en) Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof
US10399998B2 (en) Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof
US10752735B2 (en) Mixtures of cyclic branched siloxanes of the D/T type and conversion products thereof
US8598295B2 (en) Method for producing branched SiH functional polysiloxanes and the use thereof for producing SiC- and SiOC-linked, branched organomodified polysiloxanes
US8138294B2 (en) Process for preparing branched Si-H functional polysiloxanes and use thereof for preparing liquid SiC- or SiOC-linked, branched modified organomodified polysiloxanes
JP6430647B2 (ja) 有機ポリシロキサンを製造するための方法
US20130005935A1 (en) Preparing Organopolysiloxanes
US5527873A (en) Method for the preparation of silicone resins
US8686175B2 (en) Preparation of siloxanes
JPH08512234A (ja) オルガノシロキサンもしくはポリオルガノシロキサンの製造のための触媒
CA2010789C (en) Siloxane resins and method for making them
EP0611785B1 (de) Verfahren zur Herstellung von linearen Organopolysiloxanen
EP3371244B1 (de) Verfahren zur herstellung von organosiloxan
CN112041375A (zh) 用于制备草酰胺官能的硅氧烷的方法
KR20260017437A (ko) 유기폴리실록산의 생산 방법

Legal Events

Date Code Title Description
FEPP Fee payment procedure

Free format text: ENTITY STATUS SET TO UNDISCOUNTED (ORIGINAL EVENT CODE: BIG.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STPP Information on status: patent application and granting procedure in general

Free format text: DOCKETED NEW CASE - READY FOR EXAMINATION

AS Assignment

Owner name: EVONIK DEGUSSA GMBH, GERMANY

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:KNOTT, WILFRIED;DUDZIK, HORST;SIGNING DATES FROM 20181011 TO 20181019;REEL/FRAME:048228/0678

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NON FINAL ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE TO NON-FINAL OFFICE ACTION ENTERED AND FORWARDED TO EXAMINER

AS Assignment

Owner name: EVONIK OPERATIONS GMBH, GERMANY

Free format text: CHANGE OF NAME;ASSIGNOR:EVONIK DEGUSSA GMBH;REEL/FRAME:051428/0710

Effective date: 20191104

STPP Information on status: patent application and granting procedure in general

Free format text: FINAL REJECTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: ADVISORY ACTION MAILED

STPP Information on status: patent application and granting procedure in general

Free format text: RESPONSE AFTER FINAL ACTION FORWARDED TO EXAMINER

STPP Information on status: patent application and granting procedure in general

Free format text: NOTICE OF ALLOWANCE MAILED -- APPLICATION RECEIVED IN OFFICE OF PUBLICATIONS

STPP Information on status: patent application and granting procedure in general

Free format text: PUBLICATIONS -- ISSUE FEE PAYMENT VERIFIED

STCF Information on status: patent grant

Free format text: PATENTED CASE

CC Certificate of correction
MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 4TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1551); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 4